The first report on enantioselective zinc‐catalyzed aldehyde alkylation mediated by a chiral auxiliary has been revisited in the context of recent advances field. enantioselectivity alcohol formed as function progress reaction studied with four different amino alcohols. During course reaction, enantiomeric ratio, which product is formed, inverted, giving rise to enantiodivergence, phenomenon that also dependent catalyst loading. By combining these results studies nonlinear effects well other...

Self-replicating molecules provide a simple approach for investigating fundamental processes in scenarios of the emergence life. Although homochirality is an important aspect life and how it emerged, effects chirality on self-replicators have received only little attention so far. Here, we report several self-assembled with enantioselectivity that emerge spontaneously grow from enantiopure material. These require relatively small number chiral units replicators (down to eight) precursors...

An asymmetric reaction consisting of competing monomeric and dimeric catalysts may explain enantiodivergent non-linear effects.

Abstract An in‐depth study of the catalytic system, consisting enantioselective addition ZnEt 2 to benzaldehyde with (1 R ,2 S )‐(−)‐N‐Methylephedrine (NME) as chiral ligand, suggests presence dimeric and trimeric aggregates, deduced from product ee vs. catalyst loading NMR investigations ( 1 H, DOSY). Formation aggregation was excluded in earlier studies this system displays a linear ligand ‐correlation, which is usually taken an indication for absence aggregation. A subsequent theoretical...

Abstract Non‐linear effects between the enantiomeric excesses of both ligand and product are ubiquitous phenomena in asymmetric catalysis, allowing amplification (or depletion) widely used tools for mechanistic investigations. caused by catalyst aggregation; however, effect precipitation on NLEs has not been systematically investigated to date, except special cases such as ternary phase systems. In this article, we show through simulations with several literature at hand how affects shape...

Abstract Asymmetric amplification is a phenomenon that believed to play key role in the emergence of homochirality life. In asymmetric catalysis, theoretical and experimental models have been investigated provide an understanding how chiral possible, particular based on non‐linear effects. Interestingly, it has proposed quarter century ago catalysts, when not enantiopure might even be more enantioselective than their counterparts. We show here such hyperpositive effect catalysis indeed...

The transition of chemistry into biology is poorly understood. One the key questions in this how inherently divergent nature chemical reactions can be curtailed, allowing product mixtures to become enriched only a limited subset all possible reaction products. Another seemingly unrelated question whether Darwinian principles from extend chemistry. Addressing both simultaneously, we now show that evolutionary principle competitive exclusion, which states single niche stably occupied by one...

Phenomena related to asymmetric amplification are considered be key understanding the emergence of homochirality in life. In catalysis, theoretical and experimental models have been studied understand such chiral amplification, particular based on non-linear effects. Three decades after demonstration that a catalyst, when not enantiopure, could more enantioselective than its enantiopure counterpart, we show here new example nonlinear hyperpositive effect. We report our investigations...

Self-replicating molecules provide a simple approach for investigating fundamental processes in scenarios of the emergence life. Although homochirality is an important aspect life and how it emerged, effects chirality on self-replicators have received only little attention so far. Here we report several self-assembled with chiral selectivity, that emerge spontaneously grow from enantiopure material. These require relatively small number units replicators (down to 8) precursors single unit),...

Asymmetric amplification is a phenomenon that plays key role in the emergence of homochirality life. In asymmetric catalysis, theoretical and experimental models have been investigated for understanding how chiral possible, particular through non-linear effect. most remarkable cases, degree enantio-induction from non-enantiopure catalyst can be as high with an enantiopure reference system. Interestingly, it has proposed quarter century ago catalysts, when not may more enantioselective than...

Asymmetric amplification is a phenomenon that plays key role in the emergence of homochirality life. In asymmetric catalysis, theoretical and experimental models have been investigated for understanding how chiral possible, particular through non-linear effect. most remarkable cases, degree enantio-induction from non-enantiopure catalyst can be as high with an enantiopure reference system. Interestingly, it has proposed quarter century ago catalysts, when not may more enantioselective than...

In this paper, we theoretically discuss the enantiodivergent product formation in asymmetric catalysis, a process which sign of overall enantiomer switches upon change catalyst concentration. The presented model is based on catalytic system that consists both discrete and dimeric aggregated metal complexes, competition equilibrium. These concepts were then expanded to non-enantiopure catalyst, giving rise non-linear effects – special case hyperpositive where enantiomer’s enantiomeric excess....

In this paper, we theoretically discuss the enantiodivergent product formation in asymmetric catalysis, a process which sign of overall enantiomer switches upon change catalyst concentration. The presented model is based on catalytic system that consists both discrete and dimeric aggregated metal complexes, competition equilibrium. These concepts were then expanded to non-enantiopure catalyst, giving rise non-linear effects – special case hyperpositive where enantiomer’s enantiomeric excess....

In this paper, we theoretically discuss the enantiodivergent product formation in asymmetric catalysis, a process which sign of overall enantiomer switches upon change catalyst concentration. The presented model is based on catalytic system that consists both discrete and dimeric aggregated metal complexes, competition equilibrium. These concepts were then expanded to non-enantiopure catalyst, giving rise non-linear effects – special case hyperpositive where enantiomer’s enantiomeric excess....

An in-depth study of the catalytic system, consisting enantioselective addition ZnEt 2 to benzaldehyde with (1 R ,2 S )-(-)-N-Methylephedrine (NME) as chiral ligand, suggests presence dimeric and trimeric aggregates, deduced from product ee vs catalyst loading NMR investigations ( 1 H, DOSY). Formation aggregate was excluded in earlier studies this system displays a linear ligand ee-correlation, which is usually taken an indication for absence aggregation. A subsequent theoretical study,...

<p>An in-depth study of the catalytic system, consisting enantioselective addition ZnEt<sub>2</sub> to benzaldehyde with (1<i>R</i>,2<i>S</i>)-(-)-N-Methylephedrine (NME) as chiral ligand, suggests presence dimeric and trimeric aggregates, deduced from product ee vs catalyst loading NMR investigations (<sup>1</sup>H, DOSY). Formation aggregate was excluded in earlier studies this system displays a linear ligand ee-correlation, which is...